Human hair dyeing with aminophenols

ABSTRACT

THE PROCESS OF USING AND COMPOSITIONS CONTAINING DYES, WHICH ARE SUITABLE FOR ONE STEP DYEING OF HAIR AND KERATIN FIBERS WITHOUT REQUIRING THE USE OF SEPARATE DYE MODIFIERS WHICH ARE EXCEPTIONALLY COLOR STABLE, HAVING THE FORMULA:   2-(R-NH-),4-R,R4-PHENOL   IN WHICH R IS SELECTED FROM THE GROUP CONSISTING OF HYDRO GEN AND ALKYL, R1 IS SELECTED FROM THE GROUP CONSISTING OF HYDROXY AND ALKYL, AND R4 WHICH CAN BE IN POSITION 5 OR 6 ON THE RING IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, HALOGEN, HYDROXY AND ALKYL.

United States Patent 3,558,259 HUMAN HAIR DYEING WITH AMINOPHENOLSGregoire Kalopissis, Paris, and Andree Bugaut, Boulognesur-Seine,France, assignors to LOreal, Paris, France No Drawing.Continuation-impart of application Ser. No.

293,282, July 8, 1963. This application June 12, 1967,

Ser. No. 645,520

Claims priority, application France, July 11, 1962,

903,703; July 3, 1963, 940,212 Int. Cl. A61k 7/12 US. Cl. 8-10.2 9Claims ABSTRACT OF THE DISCLOSURE The process of using and compositionscontaining dyes, which are suitable for one step dyeing of hair andkeratin fibers without requiring the use of separate dye modifiers whichare exceptionally color stable, having the formula:

in which R is selected from the group consisting of hydrogen and alkyl,R, is selected from the group consisting of hydroxy and alkyl, and R,which can be in position or 6 on the ring is selected from the groupconsisting of hydrogen, halogen, hydroxy and alkyl.

This applicationvis a continuation-in-part of application 293,282 filedJuly '8, 1963, which has been abandoned.

This invention relates to improvements in processes for the dyeing ofhair and to new compositions suitable for one step keratin fiber andhair dyeing.

A number of processes for dyeing keratinic fibers and notably hair areat present known, among the most commonly employed of these processesare those which are oxidation dyes whose coloration results frompolymerization under oxidizing conditions.

In practice, the oxidation dyes employed are almost exclusively mixturesof aromatic diamines and aromatic aminophenols, generally known asbases, in combination with substances, generally called modifiers, suchas substituted or unsubstituted monoand polyphenols. It is thuspossible, by using a relatively limited number of aromatic bases andphenols, to obtain a fairly wide range of colorations, the proportionsof the various constituents which enter into the composition of the dyebath being emperically varied. However, the formation of haircoloringpigments from these mixtures results from a series of very complexchemical reactions which necessitate either the use of an oxidizingsubstance, hydrogen peroxide, or the presence of a substance having analkaline reaction, which is generally ammonia. It is also known that byincreasing the hydrogen peroxide and ammonia content there is obtainedwhat is known as a decolorizing dye, there being simultaneously produceda decoloration of the hair to be dyed and a hair coloration in thedesired shade.

It is well known that the hair-dyeing processes mentioned above havemany disadvantages arising out of the mode of formation of the pigmentsimparting the coloration to the hair. In the first place, the use ofpara-diamines is likely to produce dermatitis and even allergies incertain particularly sensitive people. On the other hand,

Patented Jan. 26, 1971 the necessary presence of alkali and of hydrogenperoxide leads to modifications of the structure of the hair, which maysometimes be undesirable. Moreover, the shades obtained by presenttechniques have a well known tendency to change in the course of time.Thus, the colorations often tend to turn towards red; this is anappreciable disadvantage.

If, in this state of the art, that is to say, when an aromatic base anda modifier are used in combination, only known bases were to beemployed, either alone or in admixture, products would be obtained whichwould have the aforesaid disadvantages in a higher degree and which, inaddition, would give very limited ranges of shades.

According to the present invention it has now been discovered that it ispossible to dye living hair without the use of the modifiers hithertotraditionally employed, provided that the aromatic bases heretoforeemployed are replaced by other selected products capable of developing acharacteristic shade, which never varies, without the aid of anoxidizing or modifying agent. It has also been discovered that it ispossible to use for this purpose solutions of these selected productshaving a slightly basic pH value, which may be as low as 7.

In this way, each of the selected bases employed develops its own shade.Consequently, an extensive range of commercially necessary shades may bemade available merely by employing a number of these products, the finalshade obtained being the component of the individual shades of thestarting materials.

The present invention provides a new hair-dyeing process which isessentially characterized by the fact that there is employed a dyeingsolution containing at least one compound having the formula:

l H U \R in which R is selected from the group consisting of hydrogenand alkyl, R, is selected from the group consisting of hydroxy andalkyl, and R, which can be in position 5 or 6 on the ring is selectedfrom the group con sisting of hydrogen, halogen, hydroxy and alkyl.Preferably when R, and R are alkyls they are low molecular Weightalkyls.

A number of preferred compounds used in the composition of thisinvention are: 4-methoxy-2-aminophenol, 6-bromo-4-methoxy-2-aminophenol,6-methyl-4-methoxy- 2-aminophenol, 4-methyl 5 hydroxy 2methylaminophenol, 4 methyl-5-hydroxy-2-aminophen0l, 5 chloro-4-hydroxy-Z-aminophenol, 5-methyl-4-hydroxy 2 aminophenol, S-methoxy 4hydroxy 2 aminophenol and 6 methyl-4-hydroxy-2-aminophenol.

Accordinwg to a feature of the invention, the dyeing solution comprisesno oxidizing agent and no modifier and its pH value is equal to orhigher than 7, viz from 7 to 11, the necessary oxidation being inducedby atmospheric oxygen.

According to a further feature of the invention, the dyeing solutioncontains, in addition to the aforesaid compound or compounds, hydrogenperoxide and an alkali, so as to efiect a decolorizing dyeing effect.However, it still contains no modifier.

The process according to the invention makes it possible to obtaingreatly improved hair dyes by virtue of the fact that it is possible touse the coloring agents without a modifier since each of the aforesaidbases develops its own shade as the result of a simple oxidation, and itis possible to obtain all the shades required in practice by simplymixing two or more of these bases.

According to a preferred method of carrying out the invention, theaforesaid compounds which are utilized for hair dyeing are stocked andbrought into solution in the form of their salts, for instance in theform. of their hydrochlorides or hydrobromides. When a base such asammonia is also added to this solution, the compounds according to theinvention are set free at the time of their utilization.

Preferred hair dye compositions are aqueous solutions containing 0.5 toby weight of the dye compound and which have a pH of 7 to 11.

In order that the invention may be more readily understood, there willnow be described by Way of illustration a number of embodiments.

EXAMPLE 1 Preparation of 6-bromo-4-methoxy-2-aminophenol An etherealsolution of ortho-bromo-para-methoxyphenol is poured drop-by-drop into asolution consisting of an excess of concentrated nitric acid and ether,the temperature being maintained below C.

The corresponding nitro derivative crystallizes as it is formed and itis sufficient to separate it and to reduce it in the usual way by meansof a mixture of tin and hydrochloric acid in order to obtain thehydrochloride of 6-bromo-4-methoxy-2-aminophenol which, whenrecrystallized from hydrochloric acid, takes the form of white crystals.

Analysis.-Calculated (percent): C, 33.00; H, 3.54; N, 5.50. Found(percent): C, 33.06-32.82; H, 3.79-3.46; N, 5.25-5.26.

EXAMPLE 2 Preparation of 5-chloro-4-hydroxy-2-aminophenol This compoundis prepared from chloro-dimethylhydroquinone which is nitrated in theusual manner with a mixture of sulphuric and nitric acids. Afterhydrolysis with caustic soda and acidification, 5-chloro-4-hydroxy-2-nitrophenol is filtered with suction. This nitro-derivative is reducedby hydrochloric acid and tin. After cooling the desired product, 'whichcrystallizes in the form of its hydrochloride with one molecule ofwater, is filtered with suction; it melts (dec.) at 163-166 C.

Analysis.-Calculated (percent): C, 33.62; H, 4.21; N, 6.55. Found(percent): C, 33.38-33.47; H, 4.22-4.18; N, 6.43-6.30.

EXAMPLE 3 Preparation of 5-methyl-4-hydroxy-2-aminophenol This productis prepared from dimethyltoluhydroquinone which is nitrated by a mixtureof sulphuric and nitric acids. The corresponding nitro-derivative thusobtained is hydrolysed by means of a sodium hydroxide solution, thensubjected to a reduction by means of a mixture of hydrochloric acid andtin; 5-methyl-4-hydroxy- 2-aminophenol is obtained in the form of itshydrochloride; it melts (dec.) at 188-190" C.

Analysis.-Calculated (percent): C, 47.87; H, 5.70; N, 7.98. Found(percent): C, 47.65-47.60; H, 5.50-5.44 N, 7.98-7.96.

EXAMPLE 4 Preparation of 4-methyl-5-hydroxy-2-aminophenol4-methyl-5-hydroxy-2-aminophenol is prepared utilizing as startingproduct 2,4,5-trihydroxytoluene which is left for a period of five daysin a 6 N ammonia solution in an air-tight container. After acidificationby hydrochloric acid and evaporation to dryness under 'vacuum, theresidue is taken up in absolute alcohol and the inorganic salts areseparated by filtration. The alcoholic filtrate is evaporated to drynessand the residue is dissolved again under heating in hydrochloric acid.On cooling the 2,4-dihydroxy aminotoluene crystallizes out with onemolecule of water in the form of its hydrochloride.

Analysis.Calculated (percent): C], 18.35; N, 7.23. Found (percent): Cl,18.58-18.40; N, 7.01-7.96.

EXAMPLE 5 Preparation of 5-methoxy-4-hydroxy-2-aminophenol This productis prepared from methoxy-dimesylhydroquinone which is nitrated in theusual manner by means of a mixture of sulphuric and nitric acids, thusobtaining 2-methoxy-5-nitrodimesylhydroquinone. This compound is thenhydrolysed with a sodium hydroxide solution at a temperature of about 50C., acidification is effected and 5-methoxy-4-hydroxy-2-nitrophenol isobtained by filtration; this product is then reduced by a mixture of tinand hydrochloric acid. On cooling the desired product crystallizes outwith one molecule of water in the form of its hydrochloride and melts at131 C. (dec.),

Analysis.Calculated (percent): C, 40.10; H, 5.72; N, 6.67. Found(percent): C, 39.51-39.85; H, 5.58-5.69; N, 6.52.

EXAMPLE 6 Preparation of 4-methyl-S-hydroxy-2-methylaminophenolTrihydroxytoluene is left for a period of four days in an aqueoussolution of monomethylamine in an air tight container. Acidification isthen effected by means of hydrochloric acid, the solution is evaporatedunder vacuum and the residue is taken up in absolute alcohol. Afterfiltration to eliminate the inorganic salts, the alcohol is evaporatedand the desired product is obtained; it is recrystallized in the form ofits hydrochloride in concentrated hydrochloric acid.

Analysis.-Calculated (percent): C, 50.66; H, 6.33; N, 7.39. Found(percent): C, 50.83-50.44; H, 6.45-6.42; N, 7.10-7.20.

EXAMPLE 7 Preparation of 6-methyl-4-methoxy-2-amlnophenol A solution ofm-cresidine is nitrated by addition of nitric acid in a mixture ofacetic acid and acetic anhydride and a mixture of two isomericnitro-derivatives is obtained. After having deacetylated by refluxingwith concentrated hydrochloric acid and after having cooled, thenon-desired isomer is eliminated by filtration. By dilution of themother-water, 6-methyl-4-hydroxy-2-nitroaniline is precipitated; itmelts at C. This compound is dissolved in a diluted sodium hydroxidesolution and it is deaminated by heating with reflux.6-methyl-4-methoxy- Z-nitrophenol is then obtained, M.P. 94.5 C. Thenitroderivative is then reduced into the corresponding amine by means ofan alkaline sodium hydrosulfite solution.6-methyl-4-methoxy-2-aminophenol is thus obtained; the hydrochloridemelts with decomposition at 2l5-222 C.

Analysis of the hydrochl0ride.Calculated (percent): C, 50.66; H, 6.33;N, 7.39. Found (percent): C, 50.20- 50.45; H, 6.15-6.08; N, 7.08-7.17.

EXAMPLE 8 Preparation of 6-methy1-4-hydroxy-2-aminophenol6-methyl-4-methoxy-2-aminophenol is refluxed with a concentratedhydrobromic acid solution. After cooling, the hydrobromide of6-methyl-4-hydroxy-2-aminophenol is filtered and separated. M.P. 225-228C. (dec.).

Analysis.Calculated (percent): C, 38.19; H, 5.54; N, 6.36. Found(percent): C, 37.97-38.22; H, 4.50-4.70; N, 6.32-6.20.

The following examples are of dyeing solutions applied in accordancewith the invention to hair on the human head.

EXAMPLE 9 A dyeing solution according to the invention is prepared bymixing:

G. 4-methoxy-2-aminophenol hydrochloride 1.75 20% ammonium laurylsulphate 6 Sodium carbonate q.s. for pH 7. Water q.s. for 100 cc.

By applying this solution to 90% White hair and leaving it in contacttherewith for 20 minutes and thereafter rinsing and washing, acopper-tinged dark blond coloration is obtained.

EXAMPLE 10 A dyeing solution according to the invention is prepared bymixing:

4-methoxy-2-aminophenol hydrochloride g 2 20% ammonium lauryl sulphate g5 20% ammonia cc 6 Diethylenetriaminepentaacetic acid, sodium salt g 0.5Water q.s. for 100 cc.

A dyeing solution according to the invention is prepared by mixing:

G 6-bromo-4-rnethoxy-Z-aminophenol hyrdochloride 2.5 Sodium carbonateq.s. for pH 7. 20% ammonium lauryl sulphate Water q.s. for 100 cc.

This solution is applied to hair containing 90% of white hairs. It isleft in contact therewith for to minutes and, after washing and rinsing,the hair has a blond coloration.

EXAMPLE 12 A dyeing solution according to the invention is prepared bymixing:

6-bromo-4-methoxy-2-aminophenol hydrochloride g 3 N/ 2 sodium carbonateq.s. for pH 7.

20% ammonium lauryl sulphate g 5 20% ammonia cc 5 Water q.s. for 100 cc.

To the mixture thusprepared are added 8 cc. of hydrogen peroxide (1305/01.).

The solution obtained is applied to light brown hair containing 70% ofwhite hairs. After a contact period of minutes, the hair is rinsed andshampooed. The hair thus treated has a gold-blond coloration.

'EXAMPLE 13 A dyeing solution according to the invention is prepared bymixing:

5 chloro 4-hydroxy 2 aminophenol, monohydrochloride, monohydrate 1.5Ammonia q.s. for pH 7. Water q.s. for 100 cc.

By applying this solution to hair containing 90% of white hairs andleaving it in contact therewith for about 20 minutes, the hair is givenafter Washing and rinsing, a blond coloration.

6 EXAMPLE 14 A dyeing solution according to the invention is prepared-by mixing:

G. 5 methyl 4 hydroxy-Z-aminophenol, monohydrochloride Ammonia q.s. forpH 7. Water q.s. for 100 cc.

By applying this solution on hair containing of white hairs and leavingit in contact therewith for 20 minutes, the hair has, after washing andrinsing, a goldenorange tint.

EXAMPLE 15 A dyeing solution according to the invention is prepared bymixing:

G. 4 methyl-5-hydroxy 2 aminophenol monohydrochloride, monohydrate 2.5Ammonia q.s. for pH 7. Water q.s. for cc.

By applying this solution to hair containing 90% of white hairs andleaving it in contact therewith for about 20 minutes, the hair has abrown violet tint.

EXAMPLE 16 A dyeing solution according to the invention is prepared bymixing:

G. 5-methoxy-4-hydroxy-2 aminophenol monohydrochloride, monohydrate 1.5Ammonia q.s. for pH 7. Water q.s. for 100 cc.

This solution is applied to hair containing 90% of white hairs and leftin contact therewith for about 20 minutes. After rinsing and shampooingthe hair is given a strong orange coloration.

EXAMPLE 17 A dyeing solution according to the invention is prepared bymixing:

G. 4-methyl-5-hydroxy-2 methyl aminophenol monohydrochloride Ammoniaq.s. for pH 7. Water q.s. for 100 cc.

This solution is applied to hair containing 90% of white hairs and leftin contact therewith for about 20 minutes. After rinsing and shampooingthe hair has a golden blond tint.

EXAMPLE 18 A dyeing solution according to the invention is prepared bymixing:

G. 6-methyl-4-methoxy-2-aminophenol hydrochloride 2.5 Ammonia q.s. forpH 7. Water q.s. for 100 cc.

This solution is applied to hair containing 90% of white hairs and leftin contact therewith for about 20 minutes. After rinsing and shampooingthe hair has a copper blond tint.

EXAMPLE 19 A dyeing solution according to the invention is prepared bymixing:

G. 6-methy1-4-hydroxy-2-aminophenol hydrobromide 2.5 Ammonia q.s. for pH9.5. Water q.s. for 100 cc.

This solution is applied to hair containing 90% white hairs and left incontact therewith for about 20 minutes. After rinsing and shampooing,the hair has a mahogany tint.

7 EXAMPLE 20 A dyeing solution according to the invention is prepared bymixing:

4-methoxy-2-aminophenol hydrochloride 0.15 6-amino-4-diethylamino-2aminophenol trihydrochloride 0.15

4-methoxy-2-arnino-(fi-hydroxyethyD-amiline 0.8

Sodium carbonate q.s. for pH 7. Water q.s. for 100 cc.

This solution is applied to light brown hair containing 80% of whitehairs. It is left in contact therewith for 20 minutes and after washingand rinsing the hair has a light gold-brown tint.

EXAMPLE 21 A dyeing solution according to the invention is prepared bymixing:

There are added to this solution at the time of use 8 cc. of hydrogenperoxide (130 vol.), whereafter it is applied to brown colored haircontaining 80% of white hairs. After a contact period of 25 minutes,rinsing and shampooing, a light red-brown coloration is obtained.

EXAMPLE 22 A dyeing solution according to the invention is prepared bymixing:

4-methoxy-2-aminophenol hydrochloride 0.5

4-methoxy-2-amino-(fl-hydroxyethyl)-aniline 0.3 -amino-4-methoxy 2aminophenol dihydrochloride 0.2

Sodium carbonate q.s. for pH 7. Water q.s. for 100 cc.

By applying this solution to light brown hair containing 90% of whitehairs and leaving it in contact therewith for 15 to 20 minutes andthereafter washing and rinsing it, there is imparted to the hair thustreated a mauvish dark ash-blond coloration.

EXAMPLE 23 The following solution is prepared:

4-methoxy-2-aminophenol hydrochloride g 2 20% ammonia cc 7 Water q.s.for 100 cc.

50 cc. of this solution are mixed with 50 cc. of hydrogen peroxide andapplied to hair containing 90% of white hairs. After 25 minutes ofcontact, the hair is shampooed, rinsed and dried. It has a flat goldenblond tint.

EXAMPLE 24 The following solution is prepared:

G. 4-methyl-5-hydroxy-2-aminophenol hydrochloride 0.54-methoxy-2-aminophenol hydrochloride 0.1

6-amino-4-methoxy-2-aminophenol hydrochloride 0.5 Sodium carbonate q.s.for pH 7. Water q.s. for 100 cc.

50 cc. of this solution are mixed with 50 cc. of a hydrogen peroxidesolution and applied to hair containing 90% of white hairs. After 25minutes of contact, the hair is shampooed, rinsed and dried.

It has a deep brown violet tint.

8 EXAMPLE 25 The following solution is prepared:

G. 4-methyl-5-hydroxy-Z-methylaminophenol hydrochlon'de 0.56-amino-4-diethylamino-2-aminophenol trihydrochloride 0.44-methoxy-2-amino- (B-hydroxyethyl) -aniline 0. 1

Sodium carbonate q.s. for pH 7. Water q.s. for 100 cc.

50 cc. of this solution are mixed with 50 cc. of a hydrogen peroxidesolution and applied to hair containing of white hairs. After 25 minutesof contact, the hair is shampooed, rinsed and dried.

It has a light golden brown tint.

What is claimed is:

l. A human hair dye composition comprising water and an effective amountof 6-brom0-4-methoxy-2-aminophenol having a pH of about 7 to 11.

2. A human hair dye composition comprising water and an effective amountof 6-methyl-4-methoxy-2-aminophenol having a pH of about 7 to 11.

3. A human hair dye composition comprising water and an efiective amountof 4-methyl-5-hydroxy-2-aminophenol having a pH of about 7 to 11.

4. A human hair dye composition comprising water and an effective amountof 4-methyl-S-hydroxy-2-methylaminophenol having a pH of about 7 to 11.

5. A human hair dye composition comprising water and an effective amountof 5-chloro-4-hydroxy-2-aminophenol having a pH of about 7 to 11.

6. A human hair dye composition comprising water and an effective amountof 5-methyl-4-hydroxy-2-aminophenol having a pH of about 7 to 11.

7. A human hair dye composition comprising water and an effective amountof 5-methoxy-4-hydroxy-2-aminophenol having a pH of about 7 to 11.

8. A human hair dye composition comprising water and an effective amountof 6-methyl=4-hydroxy-2-aminophenol having a pH of about 7 to 11.

9. The process of dyeing human hair comprising applying thereton aneffective amount of a hair dye composition comprising water and aneffective amount of a dye having the formula:

in which R is selected from the group consisting of hydrogen and methyl,R is selected from the group consisting of hydroxy, methyl and methoxy,and R, which can be in position 5 or 6 on the ring is selected from thegroup consisting of halogen, hydrogen, hydroxy, methyl and methoxy, andR, can be methoxy only when R is hydroxy, which has a pH of about 7 to11.

References Cited UNITED STATES PATENTS 3,011,858 12/1961 Lantz et al.8-10.2 3,210,252 10/1965 Blanke et al. 810.2

FOREIGN PATENTS 479,865 2/ 1938 Great Britain 260-575 ALBERT T. MEYERS,Primary Examiner V. C. CLARKE, Assistant Examiner US. Cl. X.R. 811;260-574, 575

